Anthraquinonyl thiazoles



Patented Nov. 23, 1937 UNITED STATES ANTHRAQUINONYL THIAZOLES Earl EdsonBeard, Milwaukee, Wis., assignor to E. I. du Pont de Nemours & Company,Wilmington, DeL, a corporation of Delaware No Drawing.

Application June 7, 1934,

Serial No. 729,441

8 Claims.

This invention relates to carbon compounds and to processes for theirproduction. More particularly it relates to the preparation ofderivatives of 1-nitro-anthraquinone-fi-carboxylic acid. It especiallyappertains to the substances produced by the reaction or condensation ofcarbon compounds having amino and mercapto radicals in adjacentpositions with l-nitro-anthraquinone-fi-carbonyl halides. Such productsprobably have the formula in which Z represents a carbon compoundradical, residue or nucleus.

Eckert in 1914 (Monats. fiir Chemie. 35 289) showed that by nitratinganthraquinone-betaaldehyde and oxidizing the resultantnitroanthraquinone-aldehyde that the compound 1-nitro-anthraquinone-6-carboxylic acid is produced.

It has now been found that new chemical compounds, new vat dyes, newcolored carbon compounds, new vattable compositions of matter and newintermediates may be produced by condensing (or reacting) carboncompounds especially cyclic carbon compounds having amino and mercaptoradicals in ortho (or adjacent) positions with1-nitro-anthraquinone-6-carbonyl halides.

This invention has for an object the preparation of new and valuablechemical compounds. Other objects are the preparation of carboncompounds in a very desirable physical form and in a high state ofpurity. Still further objects are to produce new vat dyes, newintermediates, new derivatives of 1-nitro-anthraquinone6-carboxylic acidand to devise new chemical processes.

A general advance in the art and other objects which will appearhereinafter are also contemplated.

The foregoing objects and related ends are accomplished in the mannerset out in the following description in which details of what isbelieved to be the best mode for carrying out the invention aredisclosed.

Specifically one method for accomplishing the 5 aforementioned objectsand obtaining the newly discovered products is by treating l-nitro-anthraquinone-G-carboxylic acid in such a way as. to produce a1-nitro-anthraquinone-6-carbonyl halide and thereafter treating theresultant com- 10 pound with an ortho-amino-mercapto carbon compounduntil a reaction has occurred and a. thiazole has been formed. In someinstances the l-nitro-anthraquinone-6-aldehyde may be usedadvantageously in the place of the corresponding acid halide. If thealdehyde is used the condensation is carried out in an acid condensingmedium such as concentrated sulfuric acid.

The invention will be further understood from a consideration of thefollowing detailed description and specific examples in which thequantities are given by weight.

PREPABATION or 1 NITRO-ANTHBAQUINONE 6 CAB- BONYL HALIDES Example I Ten(10) parts of l-nitro-anthraquinone-G- carboxylic acid were suspended in100 parts of benzene. Ten (10) parts of phosphorus pentachloride wereadded to the suspension and the whole heated at C. for one hour. Thereaction mixture was then cooled to 15 C. and filtered. The cake of theacid chloride was washed with benzene and dried.

The conversion of the acid (or its metal salt) to the carbonyl halidemay be carried out in other solvents or suspension agents for example,orthodi-chloro-benzene, nitrobenzene, toluene, monochloro-benzene andthe tri-chloro benzenes or 40 suitable mixtures of the compounds listed;and at other temperatures depending upon the particular agent used. Goodresults are also obtainable with solvent naphtha as a suspension agent.Particular mention may be made of thionyl chloride as an agent for theconversion to the desired compound. While any particular carbonyl halidemay be produced especially good results are obtainable in the case ofthe chloride and the bromide. If desired the phosphorus penta-halide maybe prepared in the solvent to be used later for the conversion of thecarboxylic acid to car- 7 bonyl halide. This may be accomplished for example by adding phosphorus tri-chloride'to the solvent and then passingastream of chlorine gas through the solution until the theoreticalamount has been added or absorbed according to the equation:

PCl3+Cl2 PCl5 TREATMENT or 1 N ITRO ANTHRAQUINONE 6 OAR- BONYL HALIDESWITH ORTHO-AMINO-IVIERGAPTAN COMPOUNDS Ten (10) parts of1-nitro-anthraquinq.)ne-6- carbonyl'chloride and. 6.4 parts of4-amino-5- mercapto-phenetole were heated together in 100 parts ofnitrobenzene at 1409-160 C. ior l to 2 hours. The reaction mass wascooled, diluted with parts of alcohol and filtered cold. Thecondensation product gives a yellow sulfuric acid solution color. rSatisfactory results are obtained in the above I procedure when a metalsalt of thernercaptan compound is used in the place of themercaptanExample III Ten (10) parts of 1-nitro-anthraquinone-6- carbonyl chlorideand 8.5 parts of lmercapto- 2-amino-anthraquinone were heated togetherin 100 parts of nitrobenzene at 1 50-180 C. for 1 to 2 hours.

7 The reaction mass was cooled, filtered at 80 0., washed withnitrobenzene and alcohol and dried. ;The condensation product produces ared-brown sulfuric acid solution color and a Bordeaux alkalinehydrosulfite vat. The same product which in this [case is thought to be5'- nitro-1: (S) 2:2- di anthraquinonyl thiazole was also producedbyj'carryirig' out theabove procedure upon the sodiurn'salt of themercaptan as a starting material. In like manner, proportionatequantities of 1:5-di-mercapto-2z6-diamino-anthraquinon'e; 1:8-di-mercapto-2 :T-diamino-anthraquinone, 2-mercapto--3-amino-anthraquinone and Bz-2-amino-Bz-l-mercaptobenzanthrone may betreated.

Ewample IV Ten (10) parts of l-nitro-anthraquinone-ficarbonyl chlorideand 8.5 parts of the sodium salt of1-mercapto-2-amino-3-chloro-anthraquinone were heated together in partsof nitrobenzene at C. for 2 to 3 hours. The reaction mass was filteredand theated as in Example III. The isolated product gives Bor- 'deauxhydrosulfitev'ats'and dissolves in concentrated sulfuric acidwith abrown color.

The corresponding 3-bromo-mercaptan may be similarly treated. Inlikermanner di-ortho-mercapto-benzidines for example thepara-aminocompound may be utilized- The inventionis not limited tocondensations involving theparticular amino-mercapto com- .75.

Q m mbe f WW h en al. ie lme Z may represent any radical containing acarbon atom. Of such compounds those in which the amino and mercaptosubstituents are attached to a benzene nucleus merit special mention.

Especially good results have been obtained.

utilizing nitrobenzene as a solvent or suspension medium for carryingout the above described reaction. Other solvents, for example,chlorinated benzenes, solvent naphtha and other inert organic solvents,having a boiling point approximating the range 150-225 C. or mixtures ofthe same may be used if desired. 'Thechoice of solvent or suspensionagent" for'c'a'rrying' out'the reaction depends largely upon theparticular substances being reacted and the convenience of the personcarrying out the reaction.

This factor may readily be decided by one skilled in the art.

The length of time during which the reactions are heated is not criticalsince heating after the completion of the reaction is not detrimental toof this invention. I

While it is not desired to limit the invention to any particular theory,it is believed that when the carbonyl halide isbrought into contact withthe ortho-amino-mercapto compound the formation of the thiazole ringtakes place in two steps.

In the first step, it is believed that a carbonyl sulfide is formed.Thereafter in a second step, water is split out with the formation ofthe desired ring. The formation of the carbonyl sulfide takes place veryreadily, even at moderate temperatures and in the absence of a solvent,for example, by vigorously grinding the reactants in a mortar. In thesecond step, in which the splitting out of water takes place,temperatures high enough .to accomplish this result, should be used.Generally speaking the temperature may vary from 100 ,C., that is atemperature which will split out water, to the boiling point ofthesolvent, but preferably temperatures below 1140? C.

and above 200 C. are not utilized. Higher temperatures are possible inpressure apparatus. The prefered temperature range in any instance maybe readily determined by the individual car- 7 rying out the reaction.

As indicated in the examples, hot filtrations are some times desirablesince they tendto efiect a purification of desired product.

The compounds produced by this invention are colored and are valuablefor the purpose of col- 2. The products which have the formula:

in which Z represents a carbon compound containing a benzene nucleus,ortho positions of said benzene nucleus being attached to the N and Satoms of the thiazole ring.

3. The process which comprises heating togetherl-nitro-anthraquinone-6-carbonyl halide andl-mercapto-2-amino-anthraquinone to form -nitro-1,(S)2,2'-di-anthraquinonyl thiazole.

-o-s g it in which Z represents the nucleus of a carbocyclic carboncompound.

6. The vat colors having the formula in which Z represents a benzeneresidue joined through ortho positions to the N and S atoms of thethiazole ring.

'7. The vat colors having the formula,

in which Z represents an anthraquinone residue. 8. The process ofpreparing thiazoles having the formula in which Z represents a carboncompound containing a benzene nucleus, ortho positions of said benzenenucleus being attached to the N and S atoms of the thiazole ring, whichcomprises condensing a l-nitro-anthraquinone-G- carbonyl halide with acarbon compound containing a benzene nucleus having amino and mercaptogroups in adjacent positions thereon. EARL EDSO-N BEARD.

Certificate of Correction Patent No. 2,099,672. November 28, 1937.

EARL EDSON BEARD It is hereby certified that errors appear in theprinted specification of the above numbered patent requiring correctionas follows: Page 2, first column, line 64, Example IV, for theated readtreated; page 3, second column, line 22, claim 7, in the formula, for

-0s 0s 11 read I! N z NZ and that the said Letters Patent should be readwith these corrections therein that the same may conform to the recordof the case in the Patent Oflice.

Signed and sealed this 22nd day of February, A. D. 1938.

[SEAL] HENRY VAN ARSDALE,

Acting Commissioner of Patents.

